Piperazinalkyl diacrylates

ABSTRACT

1. AN AMINE ACRYLATE FROM THE GROUP OF   (H2C=C(-Z)-COO-R-OOC-CH(-Z)-CH2-N)2&lt; AND   4-R&#34;-PIPERINO-CH2-CH(-Z)-COO-R-OOC-C(-Z)=CH2   WHEREIN Z IS HYDROGEN OR METHYL; R IS THE RESIDUE OF A DIOL OF THE GROUP OF SATURATED ALIPHATIC DIOLS HAVING FROM 2 TO 20 CARBON ATOMS, BICYCLO (2,2.1) HEPT-2-ENE DIOLS, CYCLOHEXYL DIOLS, PHENYL AND MONO AND DI LOWER ALKYL PHENYL DIOLS, POLYALKYLENE ETHER DIOLS HAVING FROM 2 TO 4 CARBON ATOMS IN THE ALKYLENE GROUP, ESTER GLYCOLS HAVING FROM 1 TO AN AVERAGE OF 17.5 ESTER GROUPS; AND R&#34; IS ALKYL OF FROM 1 TO 5 CARBON ATOMS.

United States Patent 3,845,056 PIPERAZINALKYL DIACRYLATES John Howard Robson and Erich Marcus, Charleston, W. Va., assignors to Union Carbide Corporation, New York, N.Y.

No Drawing. Continuation-impart of abandoned application Ser. No. 6,939, Jan. 29, 1970. This application Sept. 2, 1970, Ser. No. 69,136

Int. Cl. C07d 51/70 US. Cl. 260268 R 6 Claims ABSTRACT OF THE DISCLOSURE Amine acrylates are produced by the reaction of a diacrylate ester and an organic amine. The amine acrylates are rapidly cured by electron beam radiation as well as other types of radiation as well as by light curing means. These compounds and coating compositions containing them are highly useful in the field of protective coatings. Illustratively, the diacrylate ester of diethylene glycol is reacted with piperazine to produce piperazine diacrylate.

This application is a continuation-in-part of Serial No. 6,939, filed on Jan. 29, 1970 now abandoned.

Many different coating compositions are known in the art and there is a continuous effort to improve them. In the past many of these coatings contained volatile solvents; however, recently compositions free of such solvents have been in demand to prevent air pollution. Many such improved compositions have found commercial acceptance.

We have now found that certain amine acrylates and compositions thereof are readily cured by ultraviolet radiation, particulate or electron beam radiation or predominantly continuum light radiation. These amine acrylates can be used by themselves to produce protective coatings or they can be mixed with other known coating compositions to enhance the cure rate of these other compositions. It has been found that the amine acrylates of this invention when used in coating compositions cure at extremely rapid rates.

The amine acrylates of this invention are produced by the reaction of a polyacrylate ester, preferably a diacrylate ester with an amine having at least one hydrogen atom attached to the nitrogen atom. Thus, the suitable amines can be the primary amines or the secondary amines; further, they can be monoamines or polyamines. The preferred amine acrylates are the amine diacrylate oligomers. However, polymeric type compositions are also produced and obtained.

In its broader aspects the polyacrylate esters that can be used in the production of the amine polyacrylates are those having the structural formula:

Z i 1 Y CH2=CCOO r wherein Y is the residue of a polyol (i.e. diol, triol, tetrol) used to produce the polyacrylate ester and r can be an integer having a value of from 2 to 4 depending on whether the polyol was a diol, triol or tetrol. For simplicity, the description will direct itself mainly to those reactions using the diacrylate esters. However, this invention includes the triacrylate esters and the tetraacrylate esters. The amine acrylates produced with these higher functionality esters are generally much more viscous, usually gel-like in nature, and find preferred applications in the production of extruded shaped articles, e.g., tubes, bars, rods, films, etc. In the production of these shaped articles these higher functional amine acrylates are extruded to shape and then cured by exposure to the radiation energy.

Patented Oct. 29, 1974 The suitable diacrylate esters for producing the amine acrylates have the general structural formula:

I Z Z CH2=(I3 C O 0-R-O O C (|J=CH2 wherein Z can be hydrogen or methyl and R is the residue of the diol used to produce the diacrylate ester as hereinafter described.

The production of esters, such as the diacrylate esters, is well known to those of normal skill in the art. It is known that an acid such as acrylic acid or methacrylic acid will react with a dihydroxyl compound or polyhydroxyl compound to produce the diester, or polyacrylate ester. In a simple illustration, acrylic acid reacts with ethylene glycol to produce ethylene glycol diacrylate. The diacrylate esters can also be produced by transesterification reactions. These reactions are known in the art and the conditions under which they are carried out are so well known that they need not be set forth in detail.

The diols that are reacted with acrylic acid or methacrylic acid to produce the diacrylate esters can be any of the compounds containing two hydroxyl groups that will undergo esterification. These are well known and include the aliphatic-type diols having from two to about 20 carbon atoms, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-bu-tanediol, 1,4-butanediol, 2,3-butanediol, l,3,3-trimethyl-1,3-propanediol, Z-methyl-Z-ethyl-1,3-propanediol, 2-ethy1-l,3-hexanediol, 1,5-pentanediol, 1,10-decanediol, the 5,6-dihydroxyalkylbicyclo[2.2.1]hept-2-enes having up to about five carbon atoms in the alkyl groups thereof, e.g.,

5 ,6-dihydroxybicyclo [2.2.1 hept-Z-ene,

l-methyl-S 6-dihydroxyethylbicyclo [2. 2. 1 he pt-Z-ene, 5,6-dihydroxymethylbicyclo 2.2. 1 ]hept-2-ene, 5,6-dihydroxyethylbicyclo [2.2.1 ]hept-Z-ene, 5-hydroxy-6-hydroxyethylbicyclo [2.2.1 1 hept-Z-ene, the 5, 6-dihydroxypropylbicyclo[2.2.1 hept-Z- enes,

5 -hydroxymethyl-6-hydroxybutylbicyclo [2.2. l hept-2-ene, the 5,G-dihydroxypentylbicyclo [2.2. l hept-Z-enes,

the 5,6-dihydroxyisopropylbicyclo [2 .2. 1 hept-Z-eues, 1,4-cyclohexanedimethanol,

p-Xylylene glycol,

4 hydroxybenzyl alcohol,

1,4-cyclohexanediol;

triols such as trimethylol propane, glycerol, 1,2,6-hexanetriol; tetrols such as pentaerythritrol; and the like; the ether glycols having a molecular weight of from about 106 to about 15,000, including the heteric or block polyoxyalkylene diols, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, the polyethylene glycols and polypropylene glycols having from 2 to about 350 oxyethylene or oxypropylene, respectively, groups in the molecule, the heteric and block poly(ethylene/propylene) glycols having from 2 to about 350 oxyalkylene groups in the molecule, polytetrahydrofurar, and the like; the ester glycols having at least one ester group and two hydroxyl groups in the molecule such as 2,2-dimethyl- 3-hydroxypropyl 2,2-dimethyl-3-hydroxypropionate, and the like; the caprolaotone polyols disclosed in US. 3,169,945 that contain at least two hydroxyl groups and that have a molecular weight of from about 290 to about 20,000, preferably from about 290 to about 2,000. The compounds named and disclosed in US. 3,169,945 are incorporated herein by reference. Any dihydroxyl comformula CmH2mfCmH2mwherein m is an integer having a value of to the unsubstituted or substituted divalent cycloalkylene of the formula:

mH2m- -CmH2mthe divalent aralkylene group of the formula:

wherein p is from one to about 5 and x is zero or one; the divalent group of the formula:

p p OCDHZP) y wherein y is 0 to about 350; the divalent group of the formula:

C ,H (COOC H wherein y is 1 to about 50; and the divalent group of the formula:

-[( z)5 O]z 2)5JZ' wherein the sum of 2 plus z is from 2 to an average total value of about 20 and R is the residue of the organic functional initiator as said term has been defined and its meaning established in U.S. 3,169,945.

Illustrative of suitable diacrylate esters one can mention those listed in the following tabulation. In said tabulation the group attached to R is specifically shown as the acrylyl group. However, it can also be the methacrylyl group; this has not been shown herein order to save space and avoid repetition. The methacrylyl esters are obvious to one skilled in organic chemistry.

TABLE A Diacrylate Esters of Formula I OHz=CHC O O-OHzCH2-O O C CH=CH2 CH2=CHC O O- HCHr-O O C CH=CH2 CH2=CHC O O-GHzCHzCHzCHz-O O C CH=CH2 CH2=CHC OO-(CH2) -0 0 CCH=CH2 CH2=CHCO O-CHzCHO CHzCHO O C CH=CH2 CH3 CH3 O O C CH=CH2 The amines reacted with the diacrylate ester compounds can be any primary or secondary amine, they can be monoamines or polyamines and they can be aliphatic or aromatic, cyclic or acyclic. The suitable amines are those containing at least one reactive hydrogen atom attached to the amine nitrogen atom. Illustrative thereof are the unsubstituted and substituted amines of the following formulas:

wherein R is a linear or branched alkyl having from 1 to about carbon atoms, (R"O) SiC H -wherein R' is alkyl of from 1 to 5 carbon atoms and q is an integer of from 1 to about 5, aryl or aralkyl or alkaryl containing from 6 to about 12 carbon atoms, unsubstituted or substituted cycloalkyl containing from 5 to about 10 carbon atoms; and X is a divalent oxygen atom, a divalent NH group, a divalent CR group wherein R"" can be hydrogen or alkyl of one to five carbon atoms, a divalent NR group, or a divalent group in which m can be zero to 5.

Other suitable amines are the modified piperazine compounds. These include the reaction product of piperazine or alkyl substituted piperazines with mono-epoxides such as epichlorohydrin, styrene oxide, ethylene oxide, propylene oxide, butylene oxide, cyclohexane oxide, and the like, or poly-epoxides such as diglycidyl ether of bisphenol A, 4-vinyl-l-cyclohexane dioxide, and the like; the reaction product of said piperazines with an isocyanate such as phenyl isocyanate, methyl isocyanate, tolylene diisocyanate, bis(2 isocyanatoethyl)bicyclo[2.2.1]hept-S-ene- 2,3 dicarboxylate, bis(2-isocyanatoethyl)4-cyclohexene- 1,2-dicarboxylate, and the like. In these instances only one of the NH groups of the piperazine compound is reacted and there is always an NH group available from the piperazine molecule. In illustration the product of the reaction of piperazine with styrene oxide yields and the product of the reaction with 4-vinyl-l-cyclohexene dioxide yields Illustrative of useful amines one can mention methylamine, ethylamine, isopropylamine, n-butylamien, hexylamine, neoheptylamine, Z-ethylhexylamine, decylamine,

aminomethyltrimethoxysilane, aminoethyltriethoxysilane, aminoethyltributoxysilane, aminobutyltriethoxysilane, aminopentyltriethoxysilane, aniline, tolylamine, xylylamine, naphthylamine, benzylamine, phenethylamine, cyclopentylamine, methylcyclopentylamie, cyclohexylamine, dimethylcyclohexylamine, dimethylamine, dibutylamine, dioctylamine, N-methylamine, morpholine, piperazine, 2- methylpiperazine, N-methylpiperazine, N-propylpiperazine, piperidine, Z-ethylpiperidine, 4,4-dipiperidyl, 1,3-di- (4-piperidyl)propane, 1,5-di(4-piperidyl)pentane, and the like.

One can also use a polyamine such as ethylenediamine, diethylenetriamine, xylene diamine, hexamethylenetetramine, 1,2-diaminopropane, 1,3-diaminopropane, imino-bispropylamine, and the like. In such instances one would produce a gel-like amine acrylate compound that can be extruded or molded into a shaped article and then cured by radiation. While amine acrylates produced with polyamines have been made in the past, it has not previously been known or shown that they would rapidly cure to solid, crosslinked materials by the radiation procedures discussed herein.

The amine acrylates are produced by the reaction of a diacrylate ester of formula I with the amine. This reaction is preferably carried out in an inert gas atmosphere, for example, under nitrogen or argon, to prevent or minimize unwanted side reactions. However, this is not necessary for a successful reaction.

The reaction can be carried out at a temperature of from about -30 C. or lower to about C. or higher. The preferred temperature range is from about l0 C. to about 75 C. and the most preferred range is from about 15 C. to about 40 C.

The pressure of the reaction system can be maintained at atmospheric pressure or superatmospheric pressure.

In the reaction, one of the acrylyl groups of the diacrylate ester reacts to displace the amino hydrogen atom while the second acrylyl group of the diacrylate ester is not affected. This reaction can be shown by the following equation:

with piperazine the reaction is as follows:

The molar amount of diacrylate ester charged to the reaction system can vary from about 0.9 mole to about 3 moles or more per amino hydrogen atom equivalent in the amino compound to produce the oligomers. The preferred amount of diacrylate ester is at least one mole thereof per amino hydrogen atom equivalent and it is common to use a slight excess of at least about 20 percent. A low molecular weight polymer can be produced by using a lower molar concentration of diacrylate ester; this can be as low as 0.55 mole thereof per amino hydrogen equivalent. This aspect is exemplified in Example 23.

The reaction can be carried out in the absence of a solvent or in the presence of an inert solvent. Among the suitable inert organic solvents that can be used one can mention methanol, ethanol, acetone, benzene, toluene,

xylene, hexane, octane, and the like. Any inert solvent can be used that does not interfere with the reaction. In order to minimize side reactions, the reaction is preferably carried out in the absence of light.

In carrying out the reaction the diacrylate ester can be added to the amino compound or the amino compound can be added to the diacrylate ester; the latter procedure is preferred. At the completion of the reaction, the amine acrylates are recovered as residue products; however, in some instances recovery by conventional distillation and fractionation procedures is possible. The amine acrylates can also be prepared by simultaneously spraying separate streams of the amine compound and the diacrylate ester onto a surface or into an enclosed area. In many instances the reaction is rapid and the two components quickly coreact. The means for simultaneously feeding two or more separate streams in the proper ratios are known in the art and such equipment does not constitute a part of this invention.

Among the amine acrylates of this invention are those that can be represented by the general formulas:

V i i CH2=CCOOROOCCHCHr/NR" VI 2 R i i l CH2=CCOOROOCCHCII2NR" VII i 1 CHz=CCOOROOCCHCH2-N VIII 1 CHz=CCOOROOCCHOH2-N O i IX CH2=CCO0ROOCCHCI'I2N /GR2" CH2=CCOOROOCCHCH2N NR' XI i t #1 1 [CH2=CCOOROOCCHCH;N C H2 Illustrative of typical amine acrylates produced in this invention one can mention those listed in Table B. In the left hand column of Table B is shown the diacrylate ester from Table A that was used to produce the amine acrylate and in the right hand column there is shown the amine compound that was used to produce the amine acrylate. The amine acrylates produced therefrom correspond to the compounds of Formulas V to XI inclusive as indicated. Thus, when the diacrylate ester used was Compound 1 of Table A and the amine compound was piperazine, the amine acrylate produced was CH2=CHC O O CHzCHzO O C CH2OH2- When the dimethacrylate ester of Compound 14 of Table A is reacted with n-hexylamine, the amine acrylate is ("3H CHa CH =C CO CHzCHzO OHzCHzO O C CHCH2NC5H13 This preceding description will enable any chemist skilled in the art to write out the chemical formula and understand the chemical structures and know the specific amine acrylate compounds set forth in Table B.

TABLE B.AMINES AGRYLATES Amine acrylate, formula Ciacrylate ester from Table A Amine compound type Compound:

N-methylpiperazino Piperazino ggfisssssssssess N-pentylpiperazine N-isopropylpipcrazine N-eti ylpiperazine .do XI.

do XI.

19 l,5-di(4-piperidyl)pentnno... XI.

As previously indicated the amine acrylates are readily cured by ultraviolet light radiation or electron beam radiation or high intensity predominantly continuum light radiation. The curing is very rapid and a durable protective film is formed. One can also cure the compositions in a molded or extruded form to produce intricately shaped articles such as rods, tubes, films and the like.

The coating compositions can be applied to a surface by any of the known conventional means, including the spray, curtain, dip, pad and roll-coating techniques. The substrate to be coated can be any composition; for example, wood, metal, paper, plastic, fabric, fiber, ceramic, concrete, plaster, glass, etc.

The amine acrylate-containing compositions can be cured by ionizing radiation, either particulate or nonparticulate, or non-ionizing radiation. As a suitable source of particulate radiation, one can use any source which emits electrons or charged nuclei. Particle radiation can be generated from electron accelerators such as the Van de Graaff, resonance transformers, linear accelerators, insulating core transformers, radioactive elements such as cobalt-60, strontium-90, etc. As a suitable source of nonparticulate ionizing radiation, one can use any source which emits radiation in the range of from about 10 Angstroms, to about 2000 Angstroms, preferably from about 5 10 Angstroms to about 1 Angstrom. Suitable sources are vacuum ultraviolet lamps, such as xenon or krypton arcs, mercury lamps, and radioactive elements such as cesium-137, strontiumand cobalt-60. The nuclear reactors are also known to be a useful source of radiation. As a suitable source of non-ionizing radiation, one can use any source which emits radiation of from about 2000 Angstroms to about 4500 Angstroms. Suitable sources are mercury arcs, carbon arcs, tungsten filament lamps, Xenon arcs, krypton arcs, sunlamps, lasers, and the like. All of these devices and sources are well known in the art and those familiar with the technology are fully aware of the manner in which the radiation is generated and the precautions to be exercised in its use.

The ionizing radiation dosage necessary to effect crosslinking will vary depending upon the particular polymer that is undergoing radiation, the extent of crosslinking desired, the number of crosslinkable sites available and the molecular weight of the starting polymer. The total dosage will be from about 10' rads to 10 rads, preferably from X10 rads of 10* rads. A rad is 100 ergs of ionizing energy absorbed per gram of material being irradiated.

The radiation is carried out at a temperature below the decomposition temperature of the resin undergoing treatment, generally it is preferably from about -80 to about 125 C.

The use of low to high pressure mercury lamps to generate ultraviolet light is known. The largest such mercury lamp of commercial utility is generally about five feet long having a diameter of about one to two inches with an electrical input of about kilowatts generating a typical low intensity ultraviolet light line structure (source intensity is generally no greater than about 20 kilowatts per square foot of source projected area). An appreciable period of time is generally needed for completion of a reaction when a material is exposed to the low intensity ultraviolet radiation generated from a mercury lamp.

It has been indicated that high intensity predominantly continuum light radiation can also be used to cure or crosslink the amine acrylates or compositions containing the amine acrylates.

Recently a source of light radiation emitting high intensity predominantly continuum light radiation contain ing ultraviolet, visible and infrared radiation that can be used to polymerize monomers and to crosslink polymer compositions was discovered, namely the swirl-flow plasma arc radiation source. By means of proper light filters one can selectively screen out a portion of the light radiation emitted permitting only that wavelength portion desired to reach the material being treated.

The term high intensity predominantly continuum light radiation means continuum radiation with a source intensity of at least 350 watts per square centimeter steradian (about 1000 kilowatts per square foot) having only a minor part of the energy in peaks of bandwidths less than 100 Angstrom units, with less than about percent of the light radiated having wavelengths shorter than 4,000 Angstrom units and at least about 70 percent of the light energy radiated having wavelength longer than 4,000 Angstrom units.

This light radiation is derived from an artificial source that generates high intensity predominantly continuum light radiation with a source intensity of at least about 350 watts per square centimeter steradian, as abbreviated by the term: watts cmsr said high intensity predominantly continuum artificial light radiation has about 70 percent of the light radiated at a wavelength longer than 4,000 Angstroms and less than about 30 percent of the light radiated having a wavelength shorter than 4,000 Angstroms, generally about 80 percent of the light radiated has a wavelength longer than 4,000 Angstroms and less than about 20 percent of the light radiated has a wavelength shorter than 4,000 Angstroms, and a source intensity that can vary from about 350 watts (about 1,000 kilowatts per square foot of source projected area) to about 5,000 watts (about 15,000 kilowatts per square foot of source projected area) or more per square centimeter steradian. A convenient source of high intensity predominantly continuum light radiation is a swirl-flow plasma are light radiation apparatus. The equipment for generating high intensity predominantly continuum light radiation by this means is known and available; many different forms thereof are described in the literature. A highly eflicient apparatus for obtaining high intensity predominantly continuum light radiation is the swirl-flow plasmaarc radiation source described in US. 3,364,387. The apparatus or equipment necessary for generating the light radiation is not the subject of this invention and any source or apparatus capable of generating high intensity predominantly continuum light radiation can be used.

While any artificial source of generating high intensity predominantly continuum light radiation can be used, as previously indicated the swirl-flow plasma arc radiation apparatus is most convenient. Hence, this source will be used in this application as illustrative of a means for obtaining the high intensity continuum light radiation. Any apparatus that operates according to the known principles of the swirl-flow plasma arc radiation source can be used to produce the high intensity predominantly continuum light radiation useful in the processes of this invention. These apparatuses are often known by other terms but those skilled in this art recognize that they emit high intensity predominantly continuum light radiation. The source of radiation in a 50 kilowatt swirl-flow plasma arc radiation source is an are only about four inches long enclosed in a quartz envelope about 1.5 inches in diameter. This lamp can be readily removed and refurbished and has an acceptable long lifetime. Further, a swirl-flow plasma arc radiation apparatus having a 250-kilowatt rating would be only about two or three times as large as a SO-kilowatt source. Another advantage is the absence of a need for expensive radiation shielding. Precautions required for the artificial light source include those needed to protect ones eyes from the intense visible light and from the ultraviolet light present to prevent inadvertent sunburn effect on the body.

It is to be noted that in the spectra of high intensity predominantly continuum light radiation there is a continuum of radiation throughout the entire spectral range. This type of continuum radiation in the ultraviolet range has not heretofore been obtainable from the conventional commercial mercury arcs or lamps generally available for generating ultraviolet light. The previously known means for generating ultraviolet light produced light that shows a line or peak spectrum in the ultraviolet range, it is not a continuum spectrum in the ultraviolet range. In a line spectrum the major portion of useable ultraviolet light is that portion at which the line or band in the spectrum forms a peak; in order for such energy to be useful the material or composition that is to be treated with ultraviolet radiation must be capable of absorbing at that particular wavelength range at which the peak appears. In the event the material or composition does not have the ability to absorb .at that particular wavelength range there is little or no absorption or reaction. Thus, in the event the material or composition to be treated absorbs at a particular wavelength range in one of the valleys of the spectral curve there will be little or no reaction since there is little or no ultraviolet energy to adequately excite the system. With a high intensity predominantly continuum radiation, there is :a high intensity con-tinuum radiation of ultraviolet energy across the entire ultraviolet wavelength range of the spectrum and there is generally suflicient ultraviolet energy generated at all useful ultraviolet wavelengths to enable one to carry out reactions responsive to ultraviolet radiation without the problem of selecting compounds that will absorb at the peak Wavelength bands only. With the high intensity continuum radiation now discovered one does not have the problem of being unable to react materials or compositions that absorb in the valley areas only since for all intents and purposes such valleys do not exist in high intensity continuum radiation, the high intensity radiated light energy is essentially a continuum, it is not in peak bands.

High intensity predominantly continuum light radiation is to be distinguished from low intensity ultraviolet radiation generated by commercially available low, medium and high pressure mercury arc ultraviolet lamps. These mercury arc lamps produce light emission which is primarily line or peak rather than continuum light, wherein a major part of the light appears in bands narrower than Angstrom units, and much less than 70 percent is above 4,000 Angstrom units.

As is known, high intensity predominantly continuum light radiation from a swirl-flow plasma arc radiation source is emitted from an arc genera-ted between a pair of electrodes that are lined up axially and encased in a quartz cylinder. In an embodiment a pair of concentric quartz cylinders between which cooling water or gas flows is used. A rare gas, such as argon, krypton, neon or xenon, introduced into the inner cylinder tangentially through inlets located at one end of the inner cylinder, creates 'a swirling flow or vortex which restricts the arc to a small diameter. An electrical potential applied across the electrodes causes a high density current to flow through the gas to generate a plasma composed of electrons, positively charged ions and neutral atoms. A plasma generated in the above gases produces high intensity predominantly continuum light radiation with dilfuse maxima in the region of from about 3,500 to about 6,000 Angstroms. The radiation source can also be used with reflectors or refractive optical systems to direct the high intensity predominantly continuum light radiation emanating from the arc to a particular point or direction or geometrical area.

Crosslinking with the predominantly continuum light radiation from a swirl-flow plasma 'arc radiation source is usually carried out at ambient temperature. The time necessary for curing the amine acrylate-containing compositions W-ill vary from a fraction of a second to 30 seconds or more. In some instances as much as several minutes may be required if a thick, pigmented layer is being cured. The necessary time for completion of curing is dependent upon the particular amine 'acrylate used as well as any other component that may be present in the coating composition.

The rate of curing can be enhanced by the addition of suitable pho-tosen-sitizers. Illustrative of suitable photosensitizer compounds one can mention acetophenone, propiophenone, benzophenone, xant-hone, fluorenone, benzaldehyde, fluorene, anthroquinone, triphenylamine, carbazole, 3- or 4-methylacetophenone, 3- or 4-pentylacetophenone, 3- or 4-methylbenzophenone, 3- or 4- chlorobenzophenone, 4,4'-bis( dimethylamino benzophenone, 4, 4'-dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, 3-chlorox'anthone, 3,9-dichloroxanthone, 3-chloro- 8-nonylxanthone, 3-methoxyxanthone, 3-iodo-7-methoxyxanthone, and the like. As is obvious one can use a mixture of photosensitizers. The amount of photo-sensitizer used can vary from about 0.01 to about 20 weight percent of the coating solution. A preferred amount is from about 0.1 to about weight percent, and most preferred is a concentartion of from about 0.5 to about 3 weight percent.

As previously indicated the amine acrylates, singly or in mixtures, can be blended with from 1 to about 50 weight percent or more of other coating compositions that are known to cure on exposure to radiation. The concentration of amine acrylates blended into such compositions can vary from about 1 to 99.9 weight percent of the coating composition, preferably from about 10 to about 75 weight percent. These coating compositions can also contain from about 5 to about 50 weight percent of a polymerizable solvent such as styrene or a high boiling acrylyl ester.

The high boiling acrylyl esters that are useful in this invention can contain more than one acrylyl group in the molecule; they are well known in the art and can be represented by the general formula:

wherein Z can be hydrogen or methyl; r is an integer having a value of from 1 to about 4; and Y can be Y or it can be a monovalent group such as hydrogen; alkyl of from 1 to about 18 carbon atoms (e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, Z-methylhexyl, 2,3-dimethylbutyl, neopentyl, heptyl, neohexyl, 3,3-dimethylpentyl, octyl, 2-ethylhexyl, nonyl,

decyl, etc.); alkoxyalkyl having up to about 15 carbon atoms (e.g. methoxymethyl, methoxybutyl, methoxydecyl, ethoxyethyl, ethoxyoctyl, butoxyethyl, butoxypropyl, hexoxyethyl, decoxyethyl, decoxypentyl etc.); haloalkyl, wherein the alkyl group has up to about 15 carbon atoms as defined above and the halogen can be fluorine, chlorine, bromine or iodine (e.g. chl-oromethyl, chlorodecyl,

fiuoroethyl, bromoethyl, iodomethyl, dichloroethyl, perfluoroisopropyl, trichlorobutyl, etc.); cyano; cyanoalkyl wherein the alkyl group has up to about 15 carbon atoms as defined above (e.g. cyanomethyl, cyanoethyl, cyanobu-tyl, cyanodecyl, etc.); epoxyalkyl wherein the alkyl group has up to about 15 carbon atoms as defined above (e.g. glycidyl, 4,5-epoxypentyl, 2,3-epoxycyclohexyl, etc.); aryl (e.g. phenyl, Xyly1, tolyl, naphthyl, naphthal, benzyl, etc.); aryloxyalkyl wherein the alkyl group has up to about 15 carbon atoms as defined above (e.g. 2- phenoxyethyl, 10phenoxydecyl, 2-tolyloxyethyl, 2-naphthyloxyethyl, etc.); triallcoxysilyloxyalkyl wherein the alkoxy group has from 1 to about 5 car-bon atoms and the alkyl group has up to about 15 carbon atoms as defined above (e.g. trimethoxysilyloxymethyl, trimethoxysilyloxypropyl, trimethoxysilyloxydecyl, triethoxysilyloxyethyl, triethoxysilyloxybutyl, tripropoxysilyloxyethyl, tributoxysilyloxyethyl, etc.); CONG wherein G can be hydrogen or hydrocarbyl having up to about 15 carbon atoms (e.g. N-methyl, N-ethyl, N-propyl, N-butyl, N-decyl, N,N-dimethy1, N,N-diethyl, N,N-diisobutyl, N- cyclohexyl, N,N-dicy-clohexyl, N-phenyl, N-naphthyl, N- methyl-N-phenyl, N,N-diphenyl, N-benzyl, N,N-dibenzyl, N-tolyl, etc.); dicyclopentenyl, bicyclo[2.2.1]hept-2-en5- yl; bicyclo[2.2.1]hept-2-en-5-yl; bicyclo[2.2.1]hept-2-en- 5-yl-alkyl, wherein the alkyl group has from 1 to about 4 carbon atoms (e.g. bicyclo{2.2.1]hept-2-en-5-ylmethyl, bicyclo[2.2.1]hept-2-en-5-ylpropyl, etc.). As indicated Y can also be Y; in such instances it is a polyvalent group such as a divalent -C H -group wherein p has a value of from 1 to about 10 (e.g. methylene, ethylene, propylene, isopropylene, butylene, hexylene, 2,2-dimethylbutylene, 2-ethy1hexylene, decylene, etc.);

r 2r O r Zr) v wherein r has a value of from 2 to about 4 and v has a value of from 1 to about 5000 and the oxyalkylene portion thereof can be oxyethylene, oxypropylene, 2-oxypropylene, oxybutylene, or mixed oxyalkylene groups in the same molecule, etc.;

CH CH CH2CCOOCHzC IOH2;

CH3 CH a trivalent aliphatic hydrocarbon of the formula wherein t has a valueo f from 3 to about 10 (e.g.

CH2 CI-Iz( 3HCH2-, CH CHz( )CH2, etc.);

or a trivalent aliphatic hydrocarbon of the formula wherein s has value of from 4 to about 10 (e.g.

OH2CCH2 OH CH' OHCHzCfi CH2 CH2-, etc.).

These high boiling arcylyl compounds are well known in the art and many of them are described in Vinyl and Related Polymers by C. 'E. Schildknecht, published in 1952 by John Wiley and Sons. The common knowledge of these compounds makes the specific naming thereof in this application unnecessary in view of the extensive description set forth above.

The coating compositions are produced by mixing the selected components thereof by conventional known methods. The blend can be heated, if desired, to facilitate mixing.

Coating compositions having the amine acrylate com pound present, alone or in admixture, can contain fillers, pigments and other additives conventionally present in coating compositions. These additives are so well known to those skilled in the art that they need no specific mention; nor is it necessary for an understanding of this invention to recite concentrations thereof. The same can be said of the known radiation cur-able coating compositions that can be admixed with the amine acrylates to improve the curing and crosslinking properties.

The following examples serve to further describe this invention. The structures were confirmed by nuclear magnetic resonance spectrum analysis.

Example 1 CH =CH C O OCHzCHi O CHzCHz O O CCH:CHzN

The amine acrylate was used to coat metal panels, and the coated panels were exposed to different types of radiation. When exposed to beta radiation from a 300-kilovolt electron beam accelerator under a nitrogen atmosphere, the coating was cured to a smooth surface with a 0.5-megarad dose.

A mixture of this amine acrylate with 3 weight percent of benzophenone cured in 3 seconds under a 550-watt medium-pressure mercury are. This same mixture was completely cured in 0.5 second when exposed to the predominantly continuum light radiation from a 50-kilowatt argon swirl-flow plasma arc radiation source.

Example 2 In a maner similar to that described in Example 1, 32.2 grams of diethylene glycol diacrylate was reacted with 8.6 grams of piperazine in 22 ml. of anhydrous methanol. There was recovered 42.4 grams of the liquid, colorless amine acrylate as a residue product after removal of methanol at reduced pressure The amine acrylate was blended with 3 weight percent of benzophenone and it was used to coat a steel panel. This coating cured in 0.2 second to a dry tack-free film when exposed to the predominantly continuum light radiation from a 50-kilowatt argon swirl-flow plasma arc radiation source. The coating was smooth and had good impact resistance.

Example 3 nn 'i H,: CH 0 o 0 on. com 0 o CCHzCHr-N This amine acrylate was blended with 3 weight percent of benzophenone, and the blend was applied as a coating to a steel panel. The coating cured in 1.3 seconds on exposure to the predominantly continuum light radiation from a 50-kilowatt argon swirl-flow plasma arc radiation source. The coating was smooth and had good impact resistance.

Example 4 In a manner similar to that described in Example 1, 21.2 grams of neopentyl glycol diacrylate was reacted with a solution of 10.5 grams of 1,3-di(4-piperidyl)propane in 25 ml. of anhydrous methanol. After removal of methanol under vacuum, there was recovered 32.8 grams of the liquid, colorless amine acrylate of the following structural formula:

A portion of this amine acrylate was blended with 3 weight percent of benzophenone and coated on a steel panel as a film. This coating cured in 0.8 seconds on exposure to the predominantly continuum light radiation from 50-kilowatt argon swirl-flow plasma arc radiation source. The coating was smooth and had good impact properties.

Example 5 To 42.4 grams of neopentyl glycol diacrylate there was added at 20 C., in a dropwise manner, 10.1 grams of nhexylamine. After the addition was completed, the mixture was stirred at 20 C. for 15 minutes, then heated to 40 C. and stirred for an additional 2 hours. The amine acrylate solution was a colorless mixture of the two products shown in the following formulas: the individual components were present in a ratio of 3 parts of A to 2 parts of B.

CH2=CHC O O CH2CCH2OO C CHzCH2-NC5H13 CH3 H CH CHC O O CHzC CH2OOC CHzCHzILCsHm A portion of this amine acrylates mixture was blended with 3 weight percent of benzophenone and coated on a steel panel. The coating cured in 2.4 seconds on exposure to the predominantly continuum light radiation from a 50- kilowatt argon swirl-flow plasma arc radiation source. The coating had good impact properties.

When the neopentyl glycol diacrylate was replaced with ethylene glycol diacrylate and the reaction carried out under the same conditions, there was obtained a colorless liquid solution that was a mixture of the amine acrylates having the following structural formulas:

This solution cured to a tack-free film when treated in the same manner as the immediately preceding amine acrylates mixture.

Example 6 In a manner similar to that described in Example 1, 25.44 grams of neopentyl glycol diacrylate was reacted with 10 grams of N-methylpiperazine. There was obtained 1 1 6 a colorless solution of amine acrylate having the following The amine acrylate of Example 16 has the structure: structural formula:

on. 1 CH5 CH3 1 (I; I /j CH1=CHC O O CH; C CO 0 CH2 CHzO O CCH2CI'IiN CHZ CHCOOCHzCCH2OOCCH2CH2N N-CH: I I

CH3 CH3 CH3 0 2 A portion of this amine acrylate was blended with 3 The amine acrylate of Example 17 has the structure: weight percent of 'benzophenone and coated on steel panels. The coatings cured to tack-free films in seconds [CH7=CHCOO[(CH1)5CO 0 .orncmocI-12cu,[ooo om ET on exposure to the predominantly continuum light radia- 10 1 tion from a 50-kilowatt argon swirl-flow plasma arc radiation source.

A series of experiments was carried out to produce different amine acrylates. The procedure followed was simi- O O CCHJCI'IZ] NCH:

wherein the sum of 1 plus z is an average total value of lar to that described in Exam le 1. When the amine compound was a solid it was initially dissolved in anhydrous EXAMPLE 18 methanol and slowly added to the stirred diacrylate. When A rea tor was charged with 3180 grams of neopentyl the amine was a liqud it was added in a dropwise manner glycol diacrylate and there was bubbled into the stirred the diacrylate- Methylamine Was added as a 40 Percent dicarylate 310 grams of methylamine at a temperature of aqueous solution, and the water was subsequently removed 20 C. The amine acrylate produced was a colorless liquid by azeotropic distillation with benzene. In all instances the having a Brookfield viscosity of 1175 cps. at C. This reaction was carried out under a nitrogen atmosphere and amine acrylate is a mixture of compounds having the in an amber glass reactor or a reactor wrapped in alumistructural formula:

nurn foil for the exclusion of light. The concentrations of the reactants and the amine acrylates produced are 25 i 32 shown in the following table. Also shown in this table are CHQZCIICOO CH1( ?CH;OOCCHzCI-IzNCI-IzCHzCOO on, the properties of coating on steel panels. These coatings CH3 x were obtained by blending the amine acrylate with 3 cmooccfizcHI weight percent of benzophenone and coating a steel panel. The coatings were cured by exposure to the predominantly wh r in x has value of m 1 0 mg n steel continuum light radiation from a -kilowatt argon swirl- P2111615 With 3 Weight P benlophenone and Without b51110 iflow plasma arc radiation source, phenone cured to dry films on exposure to the predomi- Reactants Coating properties Diacrylate Amine Cure Impact, in.-lb. time, Sward Adhesion, Example Name Moles Name Moles seconds Reverse Front hardness percent 1120 EtOH NaOH H2804 1. 5 Piperazine 0 1. 3 165 165 4 100 10 10 0 2. 0 Methylarninm 1. 0 1. 3 165 165 12 0 10 10 0 2 1.5 do 1.0 0.6 165 165 4 0 10 10 0 2 1. 25 1. 0 0. 5 165 165 6 100 10 10 0 2 2.0 1. 0 2. 1 165 165 6 100 10 10 0 1 1. 5 1. 0 1. 3 165 165 8 100 10 10 0 2 1. 25 1. 0 1. 2 165 165 6 100 10 10 0 2 2. 0 Methylamine 1. 0 1. 2 100 165 6 0 3 10 0 1 1.5 do 1.0 0.6 165 165 6 100 2. 0 Piperazine 1. 0 2. 0 165 165 0 100 7 0 0 1 2. 0 Methylainine 1. 0 2. 3 165 165 10 100 3 10 0 1 11 Twenty percent solution at 25 C. for 24 hours. No'rE.NPGDA=Neopent v1 glycol diacrylate; DE G D A=Diethylb Three percent solution at 25 C. [or 24 hours. one glycol diacrylate; AP'IS: Gamma-Annnopropyltriethoxysllaue DM1-lP=2, 2-Dimethyl-3-hydroxypropyl 2, Z-dimethyl-3-hydroxy-propio nate; DEGCDA=Comp0unrl 22, Table A.

Sward Hardness was determined using the procedure set nantly continuum light radiation from a SO-kilowatt argon forth on page 138 of the Paint Testing Manual published swirl-flow plasma arc light radiation source.

by Gardner Laboratory, 'Inc., PO. Box 5728, Bethesda, Md. The impact test procedure is described on page 146 EXAMPLE 19 I of the same manual. Adhesion was determined by scribing A resin Was P Pf y reacting grams of a the film with a sharp knife into ten one-eighth inch Capmlactone PQ y Which Was h reaction product of squares, pressing scotch tape firmly against the test surface one mole of tflmethylolpfopane with caplolactone to an .at a 45 angle t th square d lli h tape away average molecular weight of about 535, with 15.5 grams with one quick motion. The percent adhesion is then deof 80/20 mixture of and y dilsocyanate ttermined vi ually, and 13.9 grams of Z-hydroxyethyl acrylate. The resin The amine acrylate produced in Example 7 has the has the basic Structural formula: structure shown in Example 3. The amine acrylate of Extemples 8 to 10 has the structure: I

CH;=CI-I C 0 0 CI-I CH; 0 0 CNH l NHCO- CHZ=CH CO 0 CH1 CCHQO 0 CCHzCH NCHQ (3H3 g The amine acrylate of Examples 11 to 13 has the structure:

CIJHQ owumoo] ooHP-ootrn oH2=oHooocnzocrnoooonzom NC;I-I Si(O 02m L i 2 (B) An amine acrylate was prepared in a manner sirn- The amme acrylate of Examples 14 and 15 s the ilar to that described in Example 1 by slowly adding 25 structure: parts by weight of morpholine to parts by weight of (CH :cflfigogl-l gfi ggg gfl ooCCH CH N H 75 neopentyl glycol diacrylate contained in an amber reaci7 tor in an inert atmosphere. The amine acrylate has the structure:

CH3 CHgCHC 0 CH2+ CHIO O C CH CHrN CH3 (C) A solvent solution was prepared containing equal parts of 2-ethylhexyl acrylate and Z-butoxyethyl acrylate.

A series of coating compositions was prepared containing dilferent amounts of the resin (A), solvent solution (C) and amine acrylate (B). These coating compositions were blended with 3 weight percent benzophenone and the coatings were applied to steel panels. The coatings were cured by exposure to the predominantly continuum light radiation from a SO-kilowatt argon swirl-flow plasma arc radiation source to produce dry films. The composigun of the coatings and the exposure times are tabulated elow:

Parts Exposure Amine to cure Resin Solvent acryl ate (sec.) Sward Coating (A) (C) (B) hardness l I Glass equals 100.

7 EXAMPLE 20 i (A) resin'was prepared as describ ed in Section (A) of Example 19.'This resir' had the same basic structure as set forth'therein.

('B) An amine acrylate was prepared as described in Section (B) of Example 19, having the same basic structure as set forth therein. 7

containing 50 parts of Resin (A). Compositions l) to (7) contained 10 parts of Amine Acrylate (B). Each compositioncontained 3 parts of benzophenone. In addition, each composition contained'polyinerizable acrylate mono- A series of coating compositions was prepared, each mers as indicated in the table. The coating compositions were applied as 0.5 to 0.7 mil wet films on steel panels and cured by radiation at a distance of 3.5 inches with electrons from a 300-kilovolt, electron beam; they were also cured by exposure to the predominantly continuum light radiation from a' SO-kilowatt argon swirl-flow plasma arc radiation source at a distance of two feet from the arc and at a distance of four feet from an SO-kilowatt argon swirl-flow plasma arc radiation source.

COATING COMPOSITIONS 10 parts neopentyl glycol diacrylate Coating Exposure comp.

(6) 32 parts 2-ethoxyethyl acrylate 5 parts diethylene glycol diacrylate A a (7) 32 parts 2-ethoxyethylacrylate 5 parts neopentyl glycol diacrylate The coatings cured under the electron beamhad the following properties; all were given anleightmagarad dose.

able Reverse Chemical resistance" Coating mg. /sp Sward impact comp. 1n hardness in.-lb. 1% HzSO 50% CzHsOH *Reflux extract on with 10 percent ethanol for 24 hours.

"Scale of 10 used in all tables.

The coatings cured by exposure to the light radiation from the 5 O-kilowatt argon swirl-flow plasma arc radiation source had the following properties: All of the coatings showed a reverse impact value greater than 165 in.-lb.

Extractables, mgJsq. 111.

Chemical resistance Sward sec. hardness The coatings cured by exposure to the light radiation from the -kilowatt argon swirl-flow plasma arc radiation source had the following properties. All of the'coatings were exposed for 2.7 seconds and all showed a reverse impact ivalue greater than 165 in.-1b. I

Chemical resistance Coating Sward comp. hardness 1% HzSOr 50% 02115011 EXAMPLE 21 A series of ink formulations was prepared by blending dilferent colors of conventional ink pigments with an amine acrylate prepared as described in Example 3. In these ink formulations grams of the amine acrylate, 15 grams of ink pigment and 3 grams of benzophenone were blended together in a pebble mill. The inks were applied to steel panels and then cured by exposure to the predominantly continuum light radiation from a 50-kilowatt argon swirl-flow plasma arc radiation source. In all cases the printing inks had good impact properties and adhesion;

19 20 they were hard and glossy and they did not smear. The results "are tabulated below:

Pigment Cure Impact.

W tim Sward Name percent seconds Reverse Front hardness Adhesion H2O EtOH N110]?! H2804- Black 15 a. 2 165 165 16 100 9 9 o 2 Chrome yellow 15 1.1 165 165 2 100 10 9 0 Blu 15 1. a 165 165 6 100 5 2 o 0 15 5.5 165 165 2 90 6 0 o a. 6 165 165 12 100 10 9 o 3 I Gardner impact test. 9 Glass equals 100. Scotch tape cross-hatch test. Twenty percent solution at 25 C. for 24 hours. 9 Three percent solution at 25 C. for 24 hours. What is claimed is: 15 5. The amine acrylate as claimed in claim 1 of the 1. A11 amine acrylate from the group of formula: v

I I v 111, (13H: j IECHFCOOOROOCOHCHz-N and [CH1=CHCOOCH2|CCOOCHzCCHzOOCCHzCHz-N CH; CH: I2 I I 6. The amine acrylate as claimed in claim 1 of the CH =OCO0ROOOCHCH2N NR formulai CH: wherem om=onooocmocmooocmomN ,Ncmcmcoocm, Z is hydrogen or methyl; R is the residue of 'a diol of the group of saturated ali- CH phatic diols'having from 2 to 20 carbon atoms, bicyclo [2.2.1] heptv2-ene diols, cyclohexyl diols, phenyl and CH,0oCoH=cH, mono and di lower alkyl phenyl diols, polyalkylenc ether diols having from 2 to 4 carbon atoms in the whemin xhas avalue of from 1 to 4. alkylene group, ester glycols havlng from 1 to an average of 17.5 ester groups; and References Cited R 1s alkyl oi from 1 to 5 carbonatoms. 1 I h UNITED STATES PATENTS fofutllgl'fi amine acrylate as clarmed 1n 0 arm 1 of t e 2,421,707 6/1947 Mackemus 260 268 R 2,946,758 7/1960 Zenftman 260-268 R 3,060,226 10/ 1962 Munn 260-486 R CHFCHCOOCHzCHzOCHzCHzOOCCHzCH-N 3,12 ,480 3/1964 Karo 260-486- R 40 3,169,945 2/1965 Hostettler 260-783 I 3,326,969 6/1967 McTeer 260-486 R 3. An amme acrylate as clalmed 1n claim 1 of the 3,015,659 1/1962 Rorig C formula; 3,094,554 6/1963 Dickstein 260-482 R a I 4 3,253,018 5/ 1966 Zachry 260-486 R 3 481 963 12/1969 Simmler 260-4482 CH-CCOOROOCCHCH N I: 3,494,901 2/1970 Oertel et a1. 260-482 c v 3,514,473 5/1970 McFadden 260-486 R wherein-R and Z have the same meanings as claimed in 3,580,913 3/1971 Bodllafjllk 260-2943 claim 1.,

4. The amine acrylate as claimed in claim 1 of the DONALD DAUS, Y Exammel' f r-mul o a OH US. Cl. X.R.

106-20; 117-9331; 204-159.11, 159.16; 260-2472 B, CHFG'HCOOGHfiCHZOWCHCHPN 268 PL, 293.63, 293.88, 335, 348 c, 448.2 13, 453 11,453

AR, 482 R, 484 R, 615 P, 617 F, 631, 635, 8 50 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,845,056 Dated October 29, 1974 J, Hu Robson et al Inventor-(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3, line 32, the formula should read as follows:

- (CH2) 5COO] ZR [OCCUR-I2) 5] Z! Column 5, line 74 "n-butylamien" should read, "n-butylamine" Column 6, line 5, "methylcyclopentylamie" should read, "methylcyclopentylamine" Column 8, line 1, the main heading to Table B should read, "AMINE ACRYLATES" Column 8, line 4, in the sub-heading "ciacrylate" should read, "diacrylate" Column 12, line 59, Trivalent" should read, "tetravalent" Column 16, line 71, the sub-numeral "1,6" should read, Ill, 16"

Signed and Sealed this sixteenth D ay Of September 1975 [SEAL] Attest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer (ummixsiuncr of Parents and Trademarks 

1. AN AMINE ACRYLATE FROM THE GROUP OF 